JPH08120088A - Antistatic styrenic resin composition - Google Patents

Abstract

PURPOSE: To obtain an antistatic styrenic resin compsn. having an excellent permanent antistatic effect and, at the same time, excellent mechanical strength and appearance by incorporating a particular styrenic resin prepd. from a polyether acid and a styrene resin contg. a pendant oxazoline group. CONSTITUTION: This resin compsn. comprises a polyether acid of formula (I) or (II) (wherein R<1> represents CH3 or C2 H5 , R<2> represents a 1-8C alkyl or alkylphenyl, (n) is 6 to 2000, and (m) is 0 to 700, provided that n>=m and n+m is 6 to 2000) and a styrenic resin, with a poly(oxyalkylene) group bonded thereto, prepd. from a styrene resin contg. in its main chain a cylic oxazoline group or a cyclic oxazine group as a pendant group (a styrenic resin contg. a pendant oxazoline group). The compsn. has excellent permanent antistatic effect and, at the same time, excellent mechanical strength and appearance and, hence, can be used in fields where there is a strong demand for antistatic properties, such as the fields of electronic and electric components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene resin composition having a permanent antistatic property and excellent mechanical strength and appearance.

[0002]

2. Description of the Related Art Plastic moldings, which have been widely used for electronic and electric equipment parts, and especially styrene resin moldings, are easily charged with static electricity, and preventing dust from adhering to them has been a conventional problem. It was In recent years, there has been an increasing demand for improvement in the antistatic function of styrene resins in order to prevent the adverse effects of electrification on electronic equipment parts such as computers.

As an antistatic method for styrene resin,
Heretofore, it has been known that a surfactant is applied to the surface of a resin molded product or kneaded into a resin. However, in this method, since the surfactant used is dispersed on the resin surface, its effect is lost by washing with water, wiping, etc., and there remains a problem in the durability of the antistatic effect. Furthermore, the change in the antistatic effect due to the change in humidity in the atmosphere was large.

In recent years, as a permanent antistatic method for a styrene resin, a method of adding a conductive filler to the styrene resin, a method of kneading a hydrophilic resin, and the like have come into practical use. However, among these, the method of adding a conductive filler gives a restriction to the coloring of the resin, and the mechanical strength may be insufficient. If the amount is reduced, there is a problem that the antistatic effect becomes insufficient.

As a method of kneading the hydrophilic resin, for example, polyethylene glycol or a polyethylene glycol-polyalkylene glycol block copolymer which is easily available and forms a complex electrolyte with salts is used in a styrene matrix resin. A method of dispersing and blending with the above was known. However, in these methods, when the hydrophilic polyether is kneaded into the styrenic resin as it is, the compatibility is not sufficient and there is a problem in the appearance of the molded product, and it is difficult to obtain a sufficient antistatic effect. Met.
Further, as another method, there is known a method in which a polyether ester amide obtained by ester-bonding a hydrophilic polyether and a polyamide, a polyether amide obtained by amide bond, or the like is kneaded into a styrene resin. However, even if this is the case, the compatibility is insufficient, the mechanical strength of the resin molded product is insufficient, and it may discolor during molding, so heat resistance and hydrolysis resistance are poor, and practical defects Remained.

As described above, although many technical attempts have been made to prevent the static electricity of the styrene resin, it has a permanent antistatic effect, excellent mechanical strength, and excellent homogeneity. At present, a styrenic resin composition having a good appearance is not yet completed.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide a styrenic resin composition having an excellent permanent antistatic effect and excellent mechanical strength and appearance. To do.

[0008]

Means for Solving the Problems The gist of the present invention is to provide an antistatic styrenic resin composition with a polyether acid represented by the following general formula (I) or general formula (II) and a main chain. A poly (oxyalkylene) group obtained from a styrene resin in which a cyclic oxazoline group or a cyclic oxazine group is suspended is contained in a styrene resin having an amide ester bond.

[0009]

Embedded image

In the formula, R ¹ represents a methyl group or an ethyl group. R ² represents an alkyl group having 1 to 8 carbon atoms or an alkylphenyl group. n represents an integer of 6 to 2000, m
Represents an integer of 0 to 700, and n ≧ m, n
+ M is 6 to 2000.

The above polyether acid is represented by the above general formula (I).
A poly (oxyalkylene) diglycolic acid represented by
Alternatively, it is a monoalkoxy poly (oxyalkylene) monoglycolic acid or an alkylphenoxy poly (oxyalkylene) monoglycolic acid represented by the general formula (II).

The poly (oxyalkylene) diglycolic acid, monoalkoxypoly (oxyalkylene) monoglycolic acid and alkylphenoxypoly (oxyalkylene) monoglycolic acid are not particularly limited, and poly (oxyalkylene) glycol, Obtained by oxidizing monoalkoxy poly (oxyalkylene) monoglycol and alkylphenoxy poly (oxyalkylene) monoglycol with oxygen or nitric acid in the presence of an oxidation catalyst such as platinum group catalyst such as platinum, osmic acid and platinum palladium carbon. What is possible can be used conveniently. Among them, poly (oxyalkylene) diglycolic acid is preferably poly (oxyethylene) diglycolic acid, and monoalkoxypoly (oxyalkylene) monoglycolic acid is preferably monoalkoxypoly (oxyethylene) monoglycolic acid. The alkylphenoxypoly (oxyalkylene) monoglycolic acid is preferably alkylphenoxypoly (oxyethylene) monoglycolic acid. Of the above polyether acids,
Examples of poly (oxyethylene) diglycolic acid include "PEO acid" manufactured by Kawaken Fine Chemical Co., Ltd., and the like.

In the general formula (I) or the general formula (II), n + m is 6 to 2000. n + m is 2000
And the weight average molecular weight of the above polyether acid is about 10
When it exceeds 0000, the processability becomes insufficient, and when n + m is less than 6 and the weight average molecular weight of the polyether acid is less than about 400, the antistatic performance and the processability become insufficient. Limited to The weight average molecular weight of the polyether acid is preferably 2000 to 10
0000, and more preferably 2000 to 2000
0.

Of the above poly (oxyalkylene) diglycolic acid, the oxyethylene unit (A) and the oxypropylene unit (B) are ABA or ABA.
Block copolymerized in the state of -BA, the molar ratio of oxyethylene and oxypropylene is 2 to 5: 1, and
Those having a weight average molecular weight of 2,000 to 20,000 exhibit a particularly excellent antistatic effect.

The above-mentioned polyether acid differs in form from a colorless and transparent viscous liquid to a white wax-like semi-solid or a white paraffin-like solid depending on the molecular weight, and its melting point is 4 to.
Although it varies up to 66 ° C, it is thermoplastic and soluble in water and many kinds of organic solvents.

The content of the above polyether acid is preferably 1 to 30% by weight based on the antistatic styrene resin composition of the present invention. The content of polyether acid is 1
If the amount is less than 30% by weight, the antistatic effect becomes insufficient, and 30
When the content is more than wt%, the mechanical strength of the antistatic styrene resin composition does not reach the practically required value. More preferably, it is 3 to 10% by weight.

The antistatic styrenic resin composition of the present invention is a styrenic resin having the above polyether acid and a cyclic oxazoline group or a cyclic oxazine group suspended in the main chain (hereinafter referred to as "oxazoline pendant". (Also referred to as "styrene resin"). The oxazoline pendant styrenic resin is one in which a cyclic oxazoline group or a cyclic oxazine group is pendantly bonded to the whole or a part of the main chain of the polystyrene containing or a copolymer of a styrene monomer and another monomer. Therefore, 2-alkenyl-2 such as styrene monomer and isopropenyl oxazoline having an unsaturated group on the α-carbon
-Oxazoline or 2-alkenyl-1,3-oxazine, and if desired, can be obtained by radical copolymerization with one or more other monomers having an ethylenically unsaturated group such as butadiene and acrylonitrile. . In the above copolymerization, the total amount of styrene and the other monomer having an ethylenically unsaturated group optionally employed is 1 to 100 mol, preferably 5 to 1 mol of the monomer containing an oxazoline group or an oxazine group. It is preferable to mix it in a ratio of 50 mol. In the reaction of the oxazoline pendant styrene-based resin with the polyether acid, the cyclic oxazoline group or the cyclic oxazine group suspended in the main chain of the oxazoline pendant styrene-based resin is the carboxyl group and amide of the polyether acid. An ester bond is formed, and a poly (oxyalkylene) group is introduced into the reaction product.

The styrene resin constituting the main chain of the oxazoline pendant styrene resin is not particularly limited, and examples thereof include polystyrene; rubber-reinforced styrene resin;
Styrene-butadiene-acrylonitrile copolymer (hereinafter also referred to as "ABS resin"); styrene-butadiene-
Methyl (meth) acrylate copolymer (hereinafter also referred to as "MBS resin"); Styrene-acrylonitrile copolymer (hereinafter also referred to as "AS resin"); Styrene monomer as the main component, and, for example, methyl methacrylate , Methyl acrylate, methacrylic acid, acrylic acid, phthalic acid,
Random, block or graft copolymers obtained by copolymerizing other vinyl monomers such as maleic acid, maleimide and acrylamide; blends of rubber-reinforced styrene resin and styrene-butadiene copolymer, rubber-reinforced styrene resin and hydrogen Blends of styrene resin and other thermoplastic resin such as blends with added styrene-butadiene copolymer, polymer blends of ABS resin and polycarbonate resin, polymer blends of ABS resin and vinyl chloride resin, etc. Etc. can be mentioned. Above all,
Polystyrene and styrene-acrylonitrile copolymer are preferred.

Among the above-mentioned oxazoline pendant styrenic resins, for example, polystyrene having a cyclic oxazoline group suspended is "Epocros RP" manufactured by Nippon Shokubai Co., Ltd.
S-1001 ", Nippon Shokubai Co., Ltd.," Epocross RPS-1 "
005 "and the like, and examples of the styrene-acrylonitrile copolymer having a cyclic oxazoline group suspended therein include“ Epocros RAS-1005 ”manufactured by Nippon Shokubai Co., Ltd.

The amount of the cyclic oxazoline group or cyclic oxazine group contained in the oxazoline pendant styrene resin depends on the amount of the polyether acid compounded in the antistatic styrene resin composition of the present invention. The cyclic oxazoline group or cyclic oxazine group is from 0.6 to 1 mol per 1 mol of the carboxyl group contained in the polyether acid
It is preferably 1.3 mol. When the amount of the cyclic oxazoline group or the cyclic oxazine group is less than 0.6 mol,
A part of the blended polyether acid cannot form a chemical bond with the styrenic resin and cannot be finely and uniformly dispersed and blended in the resin composition, resulting in an insufficient antistatic effect, and
The mechanical strength of the obtained resin molded product is also lowered, and when it exceeds 1.3 mol, it is effective in improving the dispersibility of the resin and improving the compatibility, but the cost is higher than that of the effect of the present invention. It is disadvantageous in terms of. More preferably, it is 0.8 to 1.2 mol.

The antistatic styrene resin composition of the present invention may contain a normal styrene resin containing neither a cyclic oxazoline group nor a cyclic oxazine group. The usual styrene-based resin is not particularly limited, and examples thereof include polystyrene; rubber-reinforced styrene resin; A
BS resin; MBS resin; AS resin; styrene monomer and at least one selected from the group consisting of methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, phthalic acid, maleic acid, maleimide and acrylamide. A random, block or graft copolymer obtained by the above; styrene-butadiene copolymer;
Examples thereof include styrene-butadiene copolymer hydrogenated products. It is preferable that the content of the usual styrene-based resin containing neither the cyclic oxazoline group nor the cyclic oxazine group is 0 to 30% by weight.

The antistatic styrene resin composition of the present invention may contain a thermoplastic resin other than the styrene resin. The thermoplastic resin other than the styrene resin is not particularly limited, and examples thereof include polycarbonate, polymethacrylate, polyester, polyphenylene oxide, polyvinyl chloride, polyamide, and the like. Further, for example, ABS resin and polycarbonate A polymer blend with a resin, a polymer blend with an ABS resin and a vinyl chloride resin, a polymer blend with an MBS resin and polymethacrylate, a polymer blend with an AS resin and polyester, a polymer blend with an ABS resin and polyamide, It may be a polymer alloy or the like. Of these, polyvinyl chloride, polycarbonate, polymethacrylate, polyamide and polyester are preferable. The thermoplastic resin other than the styrene resin may be appropriately selected according to the purpose within a range that does not affect the antistatic effect, mechanical strength, etc. of the antistatic styrene resin composition of the present invention. it can.

The antistatic styrene resin composition of the present invention may contain an electrolyte in order to improve its antistatic effect. The electrolyte is not particularly limited, and examples thereof include an organic electrolyte and an inorganic electrolyte. The organic electrolyte is not particularly limited, and examples thereof include organic compounds having an acidic group; salts thereof such as metal salts, organic ammonium salts, and organic phosphonium salts. The organic compound having an acidic group is not particularly limited, and examples thereof include dodecylbenzene sulfonic acid, naphthalene sulfonic acid, p-toluene sulfonic acid, a condensate of naphthalene sulfonic acid and formalin, and aromatic sulfonic acid such as polystyrene sulfonic acid. An alkyl sulfonic acid such as lauryl sulfonic acid; an organic carboxylic acid such as stearic acid, lauric acid and polyacrylic acid; an organic phosphoric acid such as diphenyl phosphite.
The metal salt is not particularly limited, and examples thereof include alkali metal salts and alkaline earth metal salts of organic compounds having these acidic groups. Examples of the organic electrolyte further include quaternary ammonium salts such as trimethyloctylammonium halide, trimethyloctylammonium halide and trioctylmethylammonium halide; quaternary phosphonium salts such as amyltriphenylphosphonium halide and tetrabutylphosphonium halide. Can be mentioned. Among them, dodecylbenzene sulfonic acid alkali metal salt, stearic acid alkali metal salt, trimethyloctyl ammonium halide,
Tetrabutylphosphonium halide is preferred.

The above-mentioned inorganic electrolyte is not particularly limited, and examples thereof include silver nitrate, calcium chloride, cadmium chloride, copper sulfate, potassium bromide, potassium dihydrogen phosphate, lithium chloride, lithium bromide, lithium iodide, and hydroxide. Examples thereof include lithium, magnesium bromide, magnesium chloride, ammonium chloride, sodium bromide, sodium carbonate, sodium dihydrogen phosphate, sodium nitrate and zinc sulfate. Of these, lithium chloride, lithium bromide, lithium hydroxide and magnesium bromide are preferable.

The amount of the above electrolyte added is preferably 0 to 10% by weight with respect to the antistatic styrene resin composition of the present invention. If the addition amount exceeds 10% by weight, the mechanical strength of the molded product of the antistatic styrene resin composition of the present invention is lowered, the appearance of the molded product is deteriorated, and there is a problem of corrosion of the molding die. . More preferably, 0.05 to
It is 3% by weight.

The antistatic styrene resin composition of the present invention may further contain various additive components, if desired, within a range not impairing the object of the present invention. The additive component is not particularly limited, and examples thereof include pigments, dyes, reinforcing fillers, heat stabilizers, antioxidants, nucleating agents, lubricants, plasticizers, ultraviolet absorbers and flame retardants.

The reinforcing filler is not particularly limited, and examples thereof include fibrous substances such as carbon fiber and glass fiber;
Calcium silicate, calcium carbonate, mica, talc,
Examples thereof include glass beads and other particles such as polymers and flakes. The flame retardant is not particularly limited, and examples thereof include known ones commonly used for styrene resins such as organic halogen-based ones, organic phosphorus-based ones, and metal hydroxide-based ones. You can Further, a flame retardant aid having an action of increasing the effect of these flame retardants can be used in combination. The flame retardant aid is not particularly limited, and examples thereof include antimony compounds such as antimony trioxide and molybdenum compounds such as ammonium molybdate.

The antistatic styrenic resin composition of the present invention contains, for example, a polyether acid component in the oxazoline pendant styrenic resin component and, if desired, both a cyclic oxazoline group and a cyclic oxazine group. Not blended styrene-based resin, other thermoplastic resin other than styrene-based resin, electrolyte component, other various additive components and the like are each mixed in a desired ratio, Banbury mixer,
It can be carried out by a method such as kneading at 130 to 280 ° C. using a mixing roll, a single-screw extruder or a twin-screw extruder.

In the above-mentioned production method, the cyclic oxazoline group or cyclic oxazine group suspended in the main chain in the styrene resin component and the carboxyl group in the polyether acid are used as other compounds in the resin composition. In order to selectively react and bond without being affected, the oxazoline pendant styrene resin and the polyether acid are preliminarily heated at a temperature of 1
Melt kneading at 30 to 280 ° C. for 2 minutes to 3 hours to prepare a styrene-based resin in which polyether chains are intramolecularly or intermolecularly amide ester-bonded, and thus obtained styrene-based styrene-based resin is bonded. The resin is mixed with a usual styrene-based resin containing neither a cyclic oxazoline group nor a cyclic oxazine group, and, in some cases, an electrolyte component and various additive components used as necessary, in a desired ratio, and melted. A method of kneading can be preferably used.

Further, in the above-mentioned production method, a thermoplastic resin other than the styrene resin is blended, and the styrene copolymer and a polycarbonate resin, a polyphenylene oxide resin, a polyvinyl chloride resin, a polyamide resin or the like other than the styrene resin is blended. In the case of forming a polymer blend with another thermoplastic resin, a styrene resin in which a polyether chain is amide ester-bonded is prepared in advance, and by adopting a method of melt-kneading the thermoplastic resin to this, both A polymer alloy with good mixing and high homogeneity at the dispersion interface is obtained.

The antistatic styrenic resin composition of the present invention can be molded by a known method such as injection molding, extrusion molding, blow molding or vacuum molding which is usually used for molding thermoplastic resins.

The antistatic styrene resin composition of the present invention can be suitably used as a molding material for parts used in electronic equipment such as computers and word processors; electric equipment such as televisions and video decks.

[0033]

[Function] Polystyrene containing a cyclic oxazoline group is known to be effective as a compatibilizing agent for resins, but a styrene resin having a poly (oxyalkylene) group bonded to a cyclic oxazoline group or a cyclic oxazine group is also effective. , Has good compatibility, and when blended with other ordinary styrene-based resins and thermoplastic resins, hydrophilic poly (oxyalkylene) groups are evenly and finely dispersed in the resin, resulting in adsorption of water. The antistatic effect is large by reducing the electrical resistivity of the resin surface. Moreover, since the poly (oxyalkylene) group is chemically bonded to the polystyrene chain through the amide ester bond, the effect is permanently retained.

[0034]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 Styrene resin having poly (oxyethylene) chains bonded
Production of fat copolymer Granular polystyrene containing 5 mol% of suspended cyclic oxazoline groups having a weight average molecular weight of about 150,000 and a functional group equivalent of about 2200 (trade name: Epocros RPS-1005, manufactured by Nippon Shokubai Co., Ltd.)
120 parts by weight, 100 parts by weight of flaky poly (oxyethylene) diglycolic acid (trade name: PEO acid # 4000, manufactured by Kawaken Fine Chemicals Co., Ltd.) having a weight average molecular weight of 3700 and carboxylic acids at both ends was mixed with a mixing roll. Knead at a roll temperature of 180 ° C. for 30 minutes, then knead and extrude at 220 ° C. using a uniaxial extruder, cut,
A polystyrene-poly (oxyethylene) copolymer (hereinafter referred to as "A-1") in which a poly (oxyethylene) chain was suspended in the main chain was obtained.

Production Example 2 Poly (oxyethylene) chain-bonded styrene resin
Production of fat copolymer Granular styrene-acrylonitrile copolymer (trade name: Epocros RAS-10) containing 5 mol% of suspended cyclic oxazoline groups having a weight average molecular weight of about 200,000 and a functional group equivalent of about 2200.
05, manufactured by Nippon Shokubai Co., Ltd.) 120 parts by weight, weight average molecular weight 3
Flake-shaped poly (oxyethylene) diglycolic acid (trade name: PEO acid #
100 parts by weight of 4000, manufactured by Kawaken Fine Chemical Co., Ltd.) was kneaded with a mixing roll at a roll temperature of 180 ° C. for 30 minutes, further kneaded and extruded at 220 ° C. with a uniaxial extruder, and cut into a poly (oxy) main chain. A pellet-shaped AS resin (hereinafter referred to as "A-2") in which (ethylene) chains were bound and suspended was obtained.

Production Example 3 Production of Styrenic Resin Polybutadiene Latex (rubber particle size 0.2 μm) 40
In the presence of parts by weight (solid content), 70% by weight of methyl methacrylate, 25% by weight of styrene, 5% by weight of acrylonitrile.
60 parts by weight of the monomer mixture of Example 1 was subjected to a process of each step of emulsion polymerization, coagulation, neutralization, washing, filtration and drying by a known method to obtain a powdered MBS resin (hereinafter referred to as "B-2").
I got).

Production Example 4 Production of Styrenic Resin Polybutadiene Latex (rubber particle size 0.2 μm) 40
In the presence of parts by weight (solid content), 60 parts by weight of a monomer mixture of 75% by weight of styrene and 25% by weight of acrylonitrile were subjected to the steps of emulsion polymerization, coagulation, neutralization, washing, filtration and drying by known methods. A powdered ABS resin (hereinafter referred to as "B-3") was obtained.

Production Example 5 Production of Styrene Resin A monomer mixture of 75% by weight of styrene and 25% by weight of acrylonitrile was copolymerized by a known method to obtain powder A.
S resin (hereinafter referred to as "B-4") was obtained.

Production Example 6 Production of Styrenic Resin A powdery styrene-methyl methacrylate copolymer (MMA-St) is prepared by copolymerizing a monomer mixture of 55% by weight of methyl methacrylate and 45% by weight of styrene by a known method.
Copolymer resin) (hereinafter referred to as "B-5") was obtained.

Example 1 As a styrene resin containing neither a cyclic oxazoline group nor a cyclic oxazine group (hereinafter referred to as "styrene resin"), 8% by weight of polybutadiene was used.
Contains rubber-reinforced polystyrene (hereinafter referred to as "B-
1 "), 80 parts by weight, poly (oxyalkylene) chain-bonded styrene resin copolymer (hereinafter referred to as" POA-bonded resin "), 20 parts by weight of A-1, and an electrolyte. 1.0 part by weight of lithium stearate (hereinafter referred to as "C-1") is blended, melt-kneaded at a cylinder temperature of 220 ° C. using an extruder, extruded, and cooled to form a pellet of a styrene resin composition. It was created. This pellet was injection-molded using an injection molding machine at a cylinder temperature of 215 ° C. and a mold temperature of 60 ° C. to obtain a resin molded product test piece.

Evaluation Method The obtained resin molded product test piece was measured and evaluated for the following items. The results are shown in Table 1. 1. Tensile Yield Strength and Elongation Measured at 23 ° C. and 50% relative humidity according to ASTM D 638 using 1/8 inch thick dumbbell strips. 2. Flexural modulus was measured according to ASTM D 790 using a 1/4 inch thick test piece at 23 ° C. and 50% relative humidity. 3. Izod impact strength Measured at 23 ° C. and 50% relative humidity according to ASTM D 256 using a half-inch thick notched test piece. 4. Surface resistance value A disk-shaped test piece having a thickness of 2 mm and a diameter of 40 mm was used to measure a test piece with a Takeda Riken TR-8601 type super insulation resistance meter.
The surface resistance value after 1 minute of voltage application was measured at a temperature of 50 ° C., a relative humidity of 50% and an applied voltage of 500 V for the values before and after washing of the test piece. The value before washing is 23 ° C after molding the test piece,
The measurement was carried out after holding for 24 hours in a relative humidity of 50%. After washing with water, the test piece was ultrasonically washed at 30 ° C. for 30 minutes, and then the surface water was wiped off to obtain 23 ° C. and a relative humidity of 5
It was measured after being kept at 0% for 24 hours. 5. Charge half time Using a static Honest meter (manufactured by Shishido Shokai) at 23 ° C, relative humidity 50%, applied voltage of 10 kV, the initial voltage of the test piece after a voltage application time of 30 seconds, and the voltage of the test piece is half the initial voltage. The time to reach was measured. 6. The surface smoothness of the appearance test piece was visually observed.

Example 2 Example 1 was repeated except that the styrene resin and the POA-bonded resin were of the types and formulations shown in Table 1 and lithium chloride (hereinafter referred to as "C-2") was used as the electrolyte.
A resin molded product test piece was obtained, measured and evaluated in the same manner as in (1). The results are shown in Table 1. In the table, "part" represents part by weight.

Examples 3 to 7 Resin molded article test pieces were obtained and measured in the same manner as in Example 1 except that the styrene type resin, the POA binding resin and the electrolyte were used in the types and formulations shown in Table 1. evaluated. The results are shown in Table 1. In the table, "part" represents part by weight.

Example 8 The POA binding resin and the electrolyte were prepared in the types and formulations shown in Table 1, and as the styrene resin, a blend of ABS resin and polycarbonate resin (EXCELLOY CB-10, manufactured by Nippon Synthetic Rubber Co., Ltd.) This is called "B-6")
A resin molded article test piece was obtained, measured and evaluated in the same manner as in Example 1 except that The results are shown in Table 1.
In the table, "part" represents part by weight.

Example 9 10.0 g of platinum and 2.5 g of palladium were added to 30 ml of aqua regia.
The chloroplatinic acid and palladium chloride obtained by evaporating the remaining acid to dryness were dissolved in 180 ml of a 5% hydrochloric acid aqueous solution. Commercial activated carbon (pore volume 1.5 ml / g) 200 g
Was suspended in 1.5 L of a 1/4 N sodium carbonate aqueous solution, and the whole amount of the above hydrochloric acid aqueous solution of chloroplatinic acid and palladium chloride was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 1 hour and further at 80 ° C. for 2 hours. Then, chloroplatinic acid and palladium chloride were adsorbed on the activated carbon. To this, 20 ml of 38% formalin solution was added and maintained at 80 ° C. for 1 hour, reduced, filtered, washed with water and dried to obtain a carbon-supported platinum palladium catalyst. 2000 g of an aqueous solution containing 100 g of this catalyst and 1000 g of oxyethylene-oxypropylene block copolymer glycol having a weight average molecular weight of about 6000 and a molar ratio of oxyethylene and oxypropylene of 2: 1 was added to a 5 L autoclave, and pressurized air was used. Pressure 10kg /
cm ^2, and oxidized at a temperature 90 ° C. 7 hours, both ends oxyethylene weight average molecular weight of about 6000 is a carboxylic acid - oxy propylene block copolymer dicarboxylic acids. 10 parts by weight of this dicarboxylic acid and 8 parts by weight of polystyrene (trade name Epocros RPS-1005, manufactured by Nippon Shokubai Co., Ltd.) having a weight average molecular weight of about 150,000 and containing about 5 mol% of a suspended cyclic oxazoline group are mixed with a mixing roll. Was kneaded for 5 minutes at a roll temperature of 200 ° C., and 100 parts by weight of styrene-acrylonitrile copolymer resin (styrene 75% by weight, acrylonitrile 25% by weight) and 1.2 parts by weight of sodium polystyrene sulfonate were added thereto. After kneading for 5 minutes, it was extruded using a uniaxial extruder and cut to obtain a pellet-shaped resin composition. Using an injection molding machine, the pellets were heated to a cylinder temperature of 220 ° C and a mold temperature of 60 ° C.
Injection molding was carried out to obtain a resin molded product test piece. The obtained resin molded product test piece was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 6 Styrenic resins and electrolytes were mixed in the formulations and types shown in Table 2 and a mixing roll was used to obtain a roll temperature of 205.
A resin molded product test piece was obtained in the same manner as in Example 1 except that the resin composition pellets were prepared by kneading at 0 ° C, further extruding at a cylinder temperature of 220 ° C using a uniaxial extruder, cooling and cutting. , Measured and evaluated. The results are shown in Table 2. In the table, "part" represents part by weight.

[0048]

[Table 1]

[0049]

[Table 2]

According to the examples, the antistatic styrenic resin composition of the present invention has good compatibility with other styrenic resins and thermoplastic resins, so that it has an excellent appearance and a permanent antistatic property. It was found that the effect was exhibited and the mechanical properties were excellent.

[0051]

According to the present invention, because of the above-mentioned constitution, it is possible to provide a styrene resin composition having an excellent permanent antistatic effect and excellent mechanical strength and appearance. It is possible to provide a molding material that can be widely used in a field in which the antistatic requirements of electric parts and the like are severe.

Claims (22)

[Claims] 1. A poly (ether) obtained from a polyether acid represented by the following general formula (I) or general formula (II), and a styrene resin having a cyclic oxazoline group or cyclic oxazine group suspended in its main chain. An antistatic styrene resin composition comprising a styrene resin having an (oxyalkylene) group bonded thereto. Embedded image In the formula, R ¹ represents a methyl group or an ethyl group. R ² is
It represents an alkyl group having 1 to 8 carbon atoms or an alkylphenyl group. n represents an integer of 6 to 2000, m represents 0 to 70
Represents an integer of 0, and n ≧ m, n + m is 6 to
2000. 2. The antistatic styrene resin composition according to claim 1, wherein the polyether acid is poly (oxyalkylene) diglycolic acid. 3. The antistatic styrene resin composition according to claim 2, wherein the poly (oxyalkylene) diglycolic acid is poly (oxyethylene) diglycolic acid. 4. The polyether acid is a monoalkoxy poly (oxyalkylene) monoglycolic acid.
The antistatic styrene resin composition described. 5. The antistatic styrene resin composition according to claim 4, wherein the monoalkoxy poly (oxyalkylene) monoglycolic acid is monoalkoxy poly (oxyethylene) monoglycolic acid. 6. The antistatic styrene resin composition according to claim 1, wherein the polyether acid is an alkylphenoxypoly (oxyalkylene) monoglycolic acid. 7. The antistatic styrene-based resin composition according to claim 6, wherein the alkylphenoxypoly (oxyalkylene) monoglycolic acid is alkylphenoxypoly (oxyethylene) monoglycolic acid. 8. The content ratio of the polyether acid is 1 to 30.
The antistatic styrene-based resin composition according to claim 1, which is in a weight percentage. 9. The styrene-based resin having a cyclic oxazoline group or a cyclic oxazine group suspended therein is one having a cyclic oxazoline group or a cyclic oxazine group suspended from polystyrene. The antistatic styrene-based resin composition according to 5, 6, 7 or 8. 10. The styrene-based resin having a cyclic oxazoline group or a cyclic oxazine group suspended therein, wherein the cyclic oxazoline group or the cyclic oxazine group is suspended from a styrene-acrylonitrile copolymer. 2,
The antistatic styrene resin composition according to 3, 4, 5, 6, 7 or 8. 11. The molar ratio of the carboxyl group contained in the polyether acid and the cyclic oxazoline group or the cyclic oxazine group suspended in the main chain is 1: 0.6 to 1.3. 2, 3, 4, 5, 6, 7, 8, 9 or 10
The antistatic styrene resin composition described. 12. A styrenic resin having a poly (oxyalkylene) group bonded thereto reacts with heating a polyether acid and a styrenic resin having a cyclic oxazoline group or cyclic oxazine group suspended in its main chain. Claims 1, 2, 3, 4, 5, 6, 7, 8, which are obtained by
The antistatic styrene-based resin composition according to 9, 10, or 11. 13. The composition according to claim 1, further comprising a styrene resin containing neither a cyclic oxazoline group nor a cyclic oxazine group.
The antistatic styrene resin composition according to 0, 11 or 12. 14. A styrene-based resin containing neither cyclic oxazoline group nor cyclic oxazine group is polystyrene; rubber-reinforced styrene resin; styrene-butadiene-acrylonitrile copolymer; styrene-butadiene-
Methyl methacrylate copolymer; Styrene-acrylonitrile copolymer; Styrene monomer and at least one selected from the group consisting of methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, phthalic acid, maleic acid, maleimide and acrylamide. The antistatic styrene according to claim 13, which is at least one selected from the group consisting of a styrene-butadiene copolymer and a styrene-butadiene copolymer hydrogenated product; -Based resin composition. 15. The thermoplastic resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 further containing another thermoplastic resin.
The antistatic styrene-based resin composition according to 1, 12, 13 or 14. 16. The antistatic styrenic resin composition according to claim 15, wherein the other thermoplastic resin is at least one selected from the group consisting of polyvinyl chloride, polycarbonate, polymethacrylate, polyamide and polyester. 17. The method according to claim 1, further comprising an electrolyte.
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
The antistatic styrene-based resin composition according to 13, 14, 15 or 16. 18. The antistatic styrene resin composition according to claim 17, wherein the electrolyte is an organic electrolyte. 19. The organic electrolyte is at least one selected from the group consisting of an alkali metal salt of dodecylbenzenesulfonic acid, an alkali metal salt of stearic acid, trimethyloctylammonium halide, and tetrabutylphosphonium halide. Item 19. An antistatic styrene resin composition according to item 18. 20. The antistatic styrene resin composition according to claim 17, wherein the electrolyte is an inorganic electrolyte. 21. The inorganic electrolyte is at least one selected from the group consisting of lithium chloride, lithium bromide, lithium hydroxide, and magnesium bromide.
The antistatic styrene resin composition described in 0. 22. The content ratio of the electrolyte is 0 to 10% by weight.
The antistatic styrene-based resin composition according to claim 17, 18, 19, 20 or 21.